Laser-induced breakdown spectroscopy (LIBS) is a rapidly developing technique for chemical materials analysis. LIBS is applied for fundamental investigations, e.g., the laser plasma matter interaction, for element, molecule, and isotope analysis, and for various technical applications, e.g., minimal destructive materials inspection, the monitoring of production processes, and remote analysis of materials in hostile environment. In this review, we focus on the element analysis of industrial materials and the in-line chemical sensing in industrial production. After a brief introduction we discuss the optical emission of chemical elements in laser-induced plasma and the capability of LIBS for multi-element detection. An overview of the various classes of industrial materials analyzed by LIBS is given. This includes so-called Technology materials that are essential for the functionality of modern high-tech devices (smartphones, computers, cars, etc.). The LIBS technique enables unique applications for rapid element analysis under harsh conditions where other techniques are not available. We present several examples of LIBS-based sensors that are applied in-line and at-line of industrial production processes.

The optical emission of plasma on industrial steel samples induced by Laser Ablation-Spark Discharge-Optical Emission Spectroscopy (LA-SD-OES) and by Laser-Induced Breakdown Spectroscopy (LIBS) is investigated and correlated to the volume of ablated steel material. The 36 steel samples investigated have an iron content C(Fe) above 94 wt%. The excitation energy in LIBS (laser pulse of 55 mJ) and in LA-SD-OES (laser pulse of 5 mJ and spark discharge of 50 mJ) is the same. In LA-SD-OES, the optical emission of plasma and the size of ablation craters are very similar for all samples and a linear calibration curve for Mn is measured (R² = 0.99). In LIBS, however, a pronounced dependence of the plasma emission and of the crater volume on the steel matrix is observed and calibration curves show a strong cross-sensitivity to other elements such as Si (matrix effect). The hardness, grain size, and phase of steel samples are analyzed to correlate the matrix effect in LIBS measurements to a physical property of the specimen. The different behavior for LA-SD-OES and LIBS is probably due to different processes of sampling and plasma excitation. From our results we conclude that LA-SD-OES enables for the element analysis of industrial steel largely independent of composition and structure of samples while in LIBS the matrix effect has to be taken into account.

Femtosecond laser-induced breakdown spectroscopy (fs-LIBS) is employed to detect tiny amounts of mass ablated from macroscopic specimens and to measure chemical images of microstructured samples with high spatial resolution. Frequency-doubled fs-pulses (length 400 fs, wavelength 520 nm) are tightly focused with a Schwarzschild microscope objective to ablate the sample surface. The optical emission of laser-induced plasma (LIP) is collected by the objective and measured with an echelle spectrometer equipped with an intensified charge-coupled device camera. A second fs-laser pulse (1040 nm) in orthogonal beam arrangement is reheating the LIP. The optimization of the experimental setup and measurement parameters enables us to record single-pulse fs-LIBS spectra of 5 nm thin metal layers with an ablated mass per pulse of 100 femtogram (fg) for Cu and 370 fg for Ag films. The orthogonal double-pulse fs-LIBS enhances the recorded emission line intensities (two to three times) and improves the contrast of chemical images in comparison to single-pulse measurements. The size of ablation craters (diameters as small as 1.5 µm) is not increased by the second laser pulse. The combination of minimally invasive sampling by a tightly focused low-energy fs-pulse and of strong enhancement of plasma emission by an orthogonal high-energy fs-pulse appears promising for future LIBS chemical imaging with high spatial resolution and with high spectrochemical sensitivity.